Cubing siccative compositions



- methylol derivatives thereof.

The following examples in which the propor- Patented Dec. 15, 1942 UNITED STATE cuamcsrocarm: oou'rosrnons weueew. 'mtou Greenwich; Conn, e-un- Cyanamid or to American Company, New York.

. N. Y., a corporation of Maine Application-October is, 1030. Serial No. seam 9 cmm- (01. 100-204)- A 1' This invention relates to the acceleration of .the rate of curing or seasoning of siccative compositions such as linoleum and coating com positions. 4 An object of this invention is to provide accelerators for- 'siccative compositions which will cause such compositions to cure more rapidly. Another object of this invention is to improve the alkali resistance of linoleum floor covering compositions; 3

These and other objects are attained by incorporating in a siccative composition a substance selected from the group consisting of cyanamide,'. dicyandiamide; melamine and the tions are given as parts by weight are given by way of illustration and not in limitation.

Exsurtn 1 4 Parts by weight Binder v v 30 Wood flour '30; Whiting 20 Lithopone 20 Cyanamide 0.3

These-substances with or without a small proportion of drier. e.- g. 0.1% cobalt naphthenate;

are mixed together, e. g. in an internal mixer.

The'compacted mas which is delivered from the mixer may be disintegrated. as by a set of scratch rolls which comprises rolls having, intermeshing teeth projecting from their surfaces. The resulting material is sheeted on calender rolls or optionally it may be further mixed and disinresistance of such a composition is about 0.28 mm.

The marked, improvement obtained. with my a composition is outstanding inasmuch as I have Exunu 2 Partsbyweight;

Binder 35 Wood flour 30 Whiting .Lithopone 20 Cyanamide. 3

found it to be very difilcult to improve the alkaliresistance by even as little as- 0.01 mm.

These substances may be mixed and sheeted in the same general manner as the procedure set forth in Example 1. The resulting floor covering sheets "season" or "mature" in about three days and the seasoned' sheets have an alkali resistance 'of about 0.11,-as compared with a seasoning speed of twelve to fourteen .days and. an. alkali resistance of about 0.28 characteristicjof'similar compositions which omit the cyanamide.

" in the samegeneral manner as .the procedure set -sheetsfseason" inabout five days anti the sea- 3 -soned'fsheets have an alkali resistance of about .0218.

tegrated and then calendered. The material may be calendered on to burlapor other fibrous backing iidesired. -'The vsheeted material is Placed in a stoving oventhrough which a current-of heated air from about 70 C. to about 90- C. is circulated until the material is completely seasoned. i. e. until the sheet acquires the necessary degree of hardness;

The hardness may be measured by any of the methods generally employed in the manufacture ot linoleum. See the Federal Stock Catalogue. section 4,'part 5, vases LLL-L-l et seq. and

pages LLL-L- 361 et seqqfor the method employed herein. Thetime required for seasoning? a 2 mm. sheet oithe above composition is about six days. Theresulting "seasoned" floor covering shows improved alkali resistance. One method of determining alkali resistance is tomeasure Emulate 3 1 f Parts by weight Binder 30 Wood flour..- i e .30 Whiting 20 Lithopone 20 Dicyandiamide y 1.5

These substancesmay be mixed and shee'ted forth in Example 1. The resulting floor covering If the proportion of di'cyandiamide to about 3-parts by weight in the above formula- 7 'tion. the "seasoning speed and alkali'resistance of such compositions are not substantially diiferent from the values obtained using 1.5 parts of g dicyandiamido in said formulation.

Exsuru 4 4 Partsbyweight. Binder v I Y I 30 Wood flour 3o Whiting p 2c Lithopone v 20 Dimethylol "dicyandiar'nide 3 the dep h millimeters to which a 5% solution v of sodium hydroxide in water penetrates in'one hour at a temperature'of -'l0 I". By this method the alkali resistance of the "seasoned sheets" is about'0.18. mm. penetration.

' 'TIie-speed of :12 mm. sheet of the same mixture which, does not contain cyanamide.

is about twelve tofourteen days and the alkali This composition may be and sheeted according to the procedureof Example 1. The

sheeted composition seasons? i about six days P and has an alkali resistanceof about-Q18. I

Exaurm: 5- 4 I Partsby weight Binder Wood flour. 30.

Whiting r 2 Lithopone -20 of about 0.19.

This composition may be mixed and sheeted according to the procedure oi! Example 1. The sheeted composition seasonsfin about seven to obtainable by reacting formaldehyde with .These substances may be mixed and sheeted according to the procedure of Example 1. The

; resulting floor covering sheets season in about an alkyl or an aryl substituted phenol. The resin, wood oil and raw linseed oil are heated to; 480 F. in about twenty minutes. when the resin is dissolved, the temperature is raised to -560 F. in about ten minutes and then gradually to 590 F. and is maintained at this point tor three to four minutes or until a heavy drop from a paddle is obtained. This varnish is then checked with the bodied oil and lead acetate. cooled and thinned with mineral spirits. A medium chrome green pigment and about l-3% o! melamine (based on total weight of linseed oil) are ground with this varnish enamel until uniformly dispersed. The ratio of pigment to varnish solids should be 37.5:625. Coatings of this varnish enamel dry much more rapidly than similar comfive days.

EXAMPLE 7 Partsbyweight Binder 30 Wood flour 30 Whitin 20 Lithopone 20 Melamine 3 If these substances be mixed and sheeted according to the method described in Example 1,

the. resulting floor covering sheets "season" in about flvedays and have an alkali resistance Exams: 8- Pi t: ehicle:

f fi titanium oxide Linseed oil 30 -antimon oxide 0.04% Cometal (added %8 a zin i (gi e g cobalt naphthe- 0.0% b metal (added as lead naphthenate) The pigment and vehicle are ground together in the volume ratio or 28:72. During this grinding about 3% by weight of cyanamide (based on the vehicle) are added to the mix and ground therewith to form a uniform mixture. The resulting paint composition dries more rapidly than similar compositions which omit the added cyanamide.

E'xmu: 9

White enamel Pi ment: Vehicle:

g 75% low oil absorption 50% xylol solution oi! oxidisin titanium oxide type 20% antimony oxide Phthalic-giycerlde-dry on nicameo resin Examples 1 to 'i' are the alkyd resins which have 1 faster drying speed than that of the same coma position in which dicyandlamide is omitted.

Exunu-s 10 I N Varnish vehicle 1 ,A" .....pounds'... 100 China-wood oil gallons.- l9 Refined raw linseed oil..-- do 3 '"Q" (Gardner-Holdt) bodied linseed oil gallons-.. 3 Lead acetate poimds.. 2% Mineral spirits ..gallons. 43 Liquid drier (6% cobalt metal content) Y a ons" V4 Resin "A" may be aiatty oil soluble resin such as a phenoliormaldehyde condensate modified with rosinand ii desirable partially or completely esteriiled with glycerol or other alcohol. Other- .wise it maybe an oil soluble phenol-aldehyde 75 able.

positions which do not-include the melamine. The melamine apparently overcomes the tendency oi the phenolic resin to slow up the drying of the other varnish ingredients. The same eiiectmay be observed it melamine be added to varnishes or the like containing alkyd resins modified with phenol-formaldehyde resins.

The binders used in Examples 1 to 7 may be derived from the drying oils and may be made in any convenient well-known manner, such as the methods describedin British Patent 305,656 or the binders may comprise any or the various alkyd resins having siccative properties. For drying oil binders. linseed oil is preferable for economic reasons but other siccative oils may be used such as. for example, menhaden or fish oil, tung oil, China-wood oil, soy bean oil, perilla oil, oiticca oil, Scheiber oil, sunflower seed oil, etc. The term "siccative oil as used herein is intended to include not only the so-called drying oils but also the so-called semi-drying oils. Furother gums or resins and/or mixed with a proportion oi! the so-called mechanical oil." Either of these types of oils may be used singly ii! desired. i

In the preparation 0! the siccative oil binders it is customary to use rosin in admixture with the oil although other substances of the same type may be used, c. g., Kauri gum, Congo gum. ester gum, abietic acid and its esters, pimaric acid, etc.

Other siccative binders which may be used in siccative properties. Among these, the drying oil modified reaction products 01 maleic or iumaric acid with terpenes and polyhydric alcohols are particularly desirable. other alkyd resins which are modified withdrying oilsmay be used such as the phthalic-glyceride resins, the glycol-maleic resins, and mixed resins such as the phthalicturnariq-glycol-slyceride resins.

Instead of wood flour and/or the whiting and llthopone used in Examples 1 to "l inclusive, other or pigments may be used. Examples oi such illlers are: cork, cellulose pulp, asbestos, cottonwood tree pulp. walnut shell meaL -glass fibers. i'oliated glass, etc. Among the pigments which may be used are included: 'lithopone barytes, zinc oxide, titanium oxide, chromates, red

lead, white lead, malachite men. chrome green,

chrome yellow, Prussian blue, iron oxide, etc. Simllilfb dyes 8l1d lakes may. used if desirn is generally preferable touse drier-s in-the 2,805,215 Drcp rationot the binders. The drier is usuallysiccative oil content, is generally sufllcient, e. g. about 0.005-'-1%, although larger proportions may ing oil modified poly dric alcohol-polyb slc acid resins, the step which comprises adding to such a composition about 0.1-5% of a substance selected from the group consisting of cyanamide, dicyandiamide, melamine and the methylol derivatives thereof, said substance acting to accelerate the speed of curing of said composition.

be used if desirable. Obviously various mixtures of driers may be used.

The coating compositions shown in Examples '8 to inclusive may be modified by substituting other drying oils or other siccative alkyd resins or modified alkyd resins for those included in thev said compositions. ers, and extenders.,.may-Ibe added or substituted for those included in these compositions. The term "seasoning as applied to linoleumcompositions indicates the process of curing by Similarly other pigments, fillheating or equivalent treatment to polymerize and/or oxidize the composition to a stage wherein the 'fioor covering is sufilciently hard and re-' sistant' to abrasion to besuitable for its intended purpose and yet is still su'fiiciently flexible topermit the usual bending and rolling required of linoleum. The term "maturing is similarly used. The term "curing as applied to coating compositions indicates the process of converting -a film thereof to a dry, hard coating.

Other accelerators which may be used include methylol cyanamide and the methylol melamines. The methylol derivatives of these compounds are made by known processes of'condensing formaldehyde with the amino compound.

I have found that only a small proportion of these accelerators is generally sufiicient, e. g. 0.14%- of the siccative composition but obviously smaller or larger proportions may be used if desirable. 1

3. In a process of curing a floor covering composition containing a siccative oil binder, the step which comprises adding to such a composition about 0.1'-5% of a substance selected from the groupconsisting of cyanamide, dicyandiamide, melamine and the methylol derivatives thereof. said substance actingto accelerate the speed of curing of said composition.

4. In a process of curing a floor covering composition containing a siccative alkyd resin binder, the step which comprises adding to'such a composition about ,0.1-5% of a substance selected from the J group consisting of cyanamide, dicyandiamide, melamine and the methylol'derivatives thereof, said substance acting to accelerate the speed of curing of said composition.

5. In a process of curing a floor covering com.- position including a siccative material selected from the group consisting of drying oils and drying oil modified polyhydric alcohol-polyb'asic acid resins, the step-which comprises adding to such a composition about 0.1-5% .of cyanamide, the cyanamide acting to accelerate the speed of ouring of said composition. I

6. In a process of curing a floor covering com- I resins, the step which comprises adding to such a' composition about 0.145% of dicyandiamide, the

dicyandiamide acting. to accelerate the speed of curing said composition.

My accelerators are preferably added during v the mixing of the binderwith the fillers, etc

although they may be added before or" during the oxidation of the binder. If my accelerators r are added before or during the oxidation they appear to-inhibit somewhat the gelation of the siccative binder. It is to be noted. however, that after gelation my accelerators speed up the curing of the siccative composition.

Obviously many modifications in the processes and compositions described abovemay be made without departing from the spirit and scope of the invention as defined in the-appended claims.

I claim:

. 1 1. In aprocess of curinga composition including a siccative material selected from the group consisting of drying oilsand drying oil modified polyhydric alcohol-polybasic acid ..res-

' ins, the step which comprises adding to such a composition about .0 .1,-5% of a substance selected from the group consisting of cyanamide, 'dicyandiamide, melamine and the methylol derivatives 7. In a process of curing a fioor covering composition including a siccative material selected from the group consisting of drying oils and drying oil modified polyhydric alcohol-polybasic acid resins, the step which comprises adding to such a composition about 0.1-5% of melamine, the melamine acting to accelerate the speed of curing of said composition.

8. In a process of curing a siccative coating composition including a material selected from the group consisting of drying oils and drying oil modified polyhydric alochol-polybasic acid resins, the step which comprises adding to such a composition about 0.1-5% of a substance selected from a group consisting of cyanamide, dicyandiamide, melamine and the methylol derivatives thereof, said substance acting to accelerate the I speed of curing of said composition.

thereof, said substance acting to accelerate the.

speed of 01811180! said composition.

-2. Inaprooess for curing'afioor covering composition including a siccative matsrial selected ffromthegroupconsistingofdrrinz oilsanddry- 9. A fioor covering composition containing a siccative binder including 'a material selected from the group consisting of drying oils and drying oil modified polyhydric alcohol-polybasic acid resins, and about O l- 5% of a substance selected from the group consisting of cyanamide, dicyandiamide, melamine and the methylol derivatives thereof, said substance acting to acceleratetho.

speed of curing oi.' said composition.

' I warren w. nunsm'. 

